CN107936226B - Dendritic epoxy resin and preparation method thereof - Google Patents
Dendritic epoxy resin and preparation method thereof Download PDFInfo
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- CN107936226B CN107936226B CN201711136175.5A CN201711136175A CN107936226B CN 107936226 B CN107936226 B CN 107936226B CN 201711136175 A CN201711136175 A CN 201711136175A CN 107936226 B CN107936226 B CN 107936226B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 93
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 15
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 15
- -1 1-butylidene naphthalene monoisocyanate Chemical compound 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical group CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- XNCNNDVCAUWAIT-UHFFFAOYSA-N Methyl heptanoate Chemical group CCCCCCC(=O)OC XNCNNDVCAUWAIT-UHFFFAOYSA-N 0.000 claims description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical group CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 4
- ANJPRQPHZGHVQB-UHFFFAOYSA-N hexyl isocyanate Chemical group CCCCCCN=C=O ANJPRQPHZGHVQB-UHFFFAOYSA-N 0.000 claims description 4
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical group [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- DSWKGCIHFICHAC-UHFFFAOYSA-N methyl 3-phenylbutanoate Chemical compound COC(=O)CC(C)C1=CC=CC=C1 DSWKGCIHFICHAC-UHFFFAOYSA-N 0.000 claims description 3
- BNNWLDUOVGYRLY-UHFFFAOYSA-N methyl 5-phenylpentanoate Chemical compound COC(=O)CCCCC1=CC=CC=C1 BNNWLDUOVGYRLY-UHFFFAOYSA-N 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 239000012974 tin catalyst Substances 0.000 claims description 3
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/031—Powdery paints characterised by particle size or shape
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
- C09D5/033—Powdery paints characterised by the additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides a preparation method of dendritic epoxy resin, belonging to the technical field of epoxy resin. Mixing an epoxy resin raw material, linear chain carboxylic ester and/or linear chain isocyanate and a catalyst, and carrying out grafting reaction to obtain dendritic epoxy resin; according to the invention, active hydroxyl is fully utilized, and a grafted side chain compound is grafted to the molecular structure of the epoxy resin under the action of a chain extension catalyst, so that the whole molecular chain of the epoxy resin has a dendritic structure, the molecular regularity of the epoxy resin is reduced, the movement space of the molecular chain is enlarged, and the toughness and the impact strength of the epoxy resin are improved.
Description
Technical Field
The invention relates to the technical field of epoxy resin, in particular to dendritic epoxy resin and a preparation method thereof.
Background
Epoxy resins are organic high molecular compounds containing two or more epoxy groups, and the molecular weight of epoxy resins is generally small except for individual epoxy resins, and the epoxy resins need to be used in combination with a curing agent to form an epoxy resin cured product.
Epoxy resin cured products have a wide range of excellent properties: good mechanical property, corrosion resistance and electric insulation property. In addition, the cured epoxy resin has the advantages of controllable crosslinking density, no generation of small molecules in the curing process, low shrinkage rate and the like, so that the cured epoxy resin is widely applied to the industries of automobiles, aviation, machinery, chemical engineering and electronic appliances. However, the epoxy resin also has the defects of large internal stress, brittleness, poor impact resistance, poor toughness and the like after curing, in order to improve the toughness and the impact resistance of the epoxy resin in the prior art, two methods of (1) adding a second phase of thermoplastic plastics, rubber or rigid particles and (2) changing the chemical structure of a self-crosslinking network of the resin are usually adopted to modify the epoxy resin, however, the first method relates to the compatibility of the epoxy resin, has great requirements on the processing technology of materials and has great implementation difficulty; the second method is mainly optimized by a chemical method, and the implementation difficulty is high.
Disclosure of Invention
The invention aims to provide a preparation method of dendritic epoxy resin, which utilizes active hydroxyl in an epoxy molecular chain to connect a macromolecular branched chain in the epoxy molecular weight, thereby improving the toughness and the shock resistance of the epoxy resin. The method is simple to operate and easy to implement, and overcomes the defect of high implementation difficulty in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of dendritic epoxy resin, which comprises the following steps:
mixing an epoxy resin raw material, a grafted side chain compound and a catalyst, and carrying out grafting reaction to obtain dendritic molecular epoxy resin;
the grafting side chain compound is linear chain carboxylic ester and/or linear chain isocyanate.
Preferably, the mass ratio of the epoxy resin raw material, the grafted side chain compound and the catalyst is (90-110): (27-30): 0.1-0.5.
Preferably, the linear isocyanate has a structural formula shown in formula I:
R1-N ═ C ═ O formula I
Wherein R is1Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane.
Preferably, the linear isocyanate is hexyl monoisocyanate, octyl 6-phenyl monoisocyanate, butyl 4-phenyl monoisocyanate, 1-butylidene naphthalene monoisocyanate, 1-methyl-6-pentylidene naphthalene monoisocyanate, 4-hexylidene biphenyl monoisocyanate or 4-ethyl-4-propylidene biphenyl monoisocyanate.
Preferably, the linear carboxylic ester is a linear carboxylic methyl ester, and the structure of the linear carboxylic ester is shown in formula II:
wherein R is2Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane.
Preferably, the linear carboxylic acid methyl ester is methyl n-heptanoate, methyl 3-phenylbutyrate, methyl 5-phenylpentanoate, methyl 1-naphthyloctanoate, methyl 1-ethyl-6-butylidenylnaphthalenecarboxylate, methyl 4-hexylidenylbiphenylcarboxylate or methyl 3-ethyl-4-butylidenylbiphenylcarboxylate.
Preferably, the catalyst is one or more of organic tin, titanate and acetylacetone salt.
Preferably, the organic tin catalyst is dibutyltin oxide and/or dibutyltin dilaurate;
the titanate catalyst is tetraisopropyl titanate and/or butyl titanate;
the acetylacetone salt catalyst is zinc acetylacetonate.
Preferably, the temperature of the grafting reaction is 80-150 ℃, and the time of the grafting reaction is 1-4 h.
The invention also provides the dendritic epoxy resin prepared by the preparation method, wherein the epoxy value of the dendritic epoxy resin is 0.15-0.20 mol/100g, and the softening point is 60-80 ℃.
Has the advantages that: the invention provides a preparation method of dendritic epoxy resin, which comprises the steps of mixing an epoxy resin raw material, linear chain carboxylic ester and/or linear chain isocyanate and a catalyst, and carrying out grafting reaction to obtain the dendritic epoxy resin. According to the invention, active hydroxyl in the epoxy resin raw material is fully utilized, and the grafted side chain compound is grafted to the molecular structure of the epoxy resin under the action of the catalyst, so that the whole molecular chain of the epoxy resin has a dendritic structure, the molecular regularity of the epoxy resin is reduced, the movement space of the molecular chain is enlarged, and the toughness and the impact strength of the epoxy resin are improved.
Detailed Description
The invention provides a preparation method of dendritic epoxy resin, which comprises the following steps:
mixing an epoxy resin raw material, a grafted side chain compound and a catalyst, and carrying out grafting reaction to obtain a dendritic epoxy resin;
the grafting side chain compound is linear chain carboxylic ester and/or linear chain isocyanate.
In the invention, the mass ratio of the epoxy resin raw material, the grafted side chain compound and the catalyst is preferably (90-110): (27-30): (0.1 to 0.5), more preferably (95 to 100): (28-30): (0.2 to 0.3); the invention has no special requirement on the source of the raw materials, and the raw materials can be obtained from commercial products with the sources well known to those skilled in the art.
In the invention, the epoxy resin raw material contains hydroxyl, and a grafting side chain compound is grafted to the molecular structure of the epoxy resin raw material by utilizing active hydroxyl to form dendritic epoxy resin; the softening point of the epoxy resin raw material is preferably lower than 80 ℃, more preferably lower than 70 ℃, and the lower softening point can ensure that the raw material obtains lower viscosity, thereby being beneficial to fully stirring and uniformly mixing the materials and improving the stability of the performance of the product; the epoxy resin raw material is preferably bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin or aliphatic epoxy resin, and more preferably bisphenol A epoxy resin or bisphenol F epoxy resin; the bisphenol A epoxy resin is preferably E-20, E-24 or E-51.
In the invention, the catalyst is preferably one or more of organic tin, titanate and acetylacetone salt; the organic tin catalyst is preferably dibutyltin oxide and/or dibutyltin dilaurate; the titanate catalyst is preferably tetraisopropyl titanate and/or butyl titanate; the acetylacetone catalyst is preferably zinc acetylacetonate.
In the present invention, the grafted side chain compound is preferably a linear carboxylic acid ester and/or a linear isocyanate; wherein the structural formula of the linear isocyanate is preferably shown as formula I:
R1-N ═ C ═ O formula I
Wherein R is1Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane; the linear isocyanate is more preferably hexyl monoisocyanate, octyl 6-phenyl monoisocyanate, butyl 4-phenyl monoisocyanate, 1-butylidenylnaphthalene monoisocyanate, 1-methyl-6-pentylenenaphthalene monoisocyanate, 4-hexylenebiphenyl monoisocyanate or 4-ethyl-4-propylenebiphenyl monoisocyanate.
In the present invention, when said R is1When the alkyl group is a phenyl-substituted C3-C15 linear alkane, the number of carbon atoms of the linear alkane is preferably 5-12, and more preferably 8-10; when R is1When the alkyl group is biphenyl substituted C3-C15 linear alkane, the carbon number of the linear alkane is preferably 5-12, and more preferably 8-10; when R is1When the alkyl group is a naphthalene ring group-substituted C3-C15 linear alkane, the number of carbon atoms of the linear alkane is preferably 5-12, more preferably 8-10; when R is1When the paraffin wax is unsubstituted C3-C15 linear paraffin, the number of carbon atoms of the linear paraffin is preferably 5-12, more preferably 8-10.
In the present invention, the linear carboxylic acid ester is preferably a linear carboxylic acid methyl ester, and the structural formula of the linear carboxylic acid methyl ester is preferably shown in formula II:
wherein R is2Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane; more preferably, the linear carboxylic acid methyl ester is n-heptanoic acid methyl ester, 3-phenylbutyric acid methyl ester, 5-phenylpentanoic acid methyl ester, 1-naphthyloctanoic acid methyl ester, 1-ethyl-6-butylidenylnaphthalenecarboxylic acid methyl ester, 4-hexylidenebiphenylcarboxylic acid methyl ester or 3-Ethyl-4-butylidenebiphenylcarboxylic acid methyl ester. In the present invention, when said R is2When the alkyl group is a phenyl-substituted C3-C15 linear alkane, the number of carbon atoms of the linear alkane is preferably 5-12, and more preferably 8-10; when R is2When the alkyl group is biphenyl substituted C3-C15 linear alkane, the carbon number of the linear alkane is preferably 5-12, and more preferably 8-10; when R is2When the alkyl group is a naphthalene ring group-substituted C3-C15 linear alkane, the number of carbon atoms of the linear alkane is preferably 5-12, more preferably 8-10; when R is2When the paraffin wax is unsubstituted C3-C15 linear paraffin, the number of carbon atoms of the linear paraffin is preferably 5-12, more preferably 8-10.
In the invention, the temperature of the grafting reaction is preferably 80-150 ℃, and more preferably 100-120 ℃; the time of the grafting reaction is preferably 1 to 4 hours, and more preferably 2 to 3 hours.
In the present invention, the grafting reaction is preferably performed under stirring conditions to ensure the uniformity of grafting; the stirring speed is preferably 300-800 r/min, and more preferably 500-700 r/min.
The method has no special requirements on the adding sequence of the epoxy resin raw material, the grafted side chain compound and the catalyst, preferably, the epoxy resin raw material is placed in a closed container, the temperature is increased to 80-110 ℃, then the grafted side chain compound is added, the temperature is adjusted to the grafting temperature, and the catalyst is added for grafting reaction; according to the invention, before the epoxy resin raw material is heated to 80-110 ℃, nitrogen is preferably introduced into a closed container to remove air, so that the epoxy group is prevented from being oxidized; in the present invention, the heating method of the epoxy resin raw material and the heating method of the temperature required for the graft reaction are not particularly required, and oil bath heating is preferred.
When the grafted side chain compound is linear chain carboxylate, the invention preferably carries out vacuum treatment during the grafting reaction, the vacuum condition is preferably 1.01-20.27 KPa, a reaction container is in a vacuum state in the reaction process, and methanol obtained by the reaction can be removed in time, so that the reaction is carried out towards the direction of obtaining the dendritic epoxy resin.
When the grafted side chain compound is linear isocyanate, the reaction vessel is preferably vacuumized before the grafted side chain compound is added to remove the moisture in the epoxy resin raw material and prevent the isocyanate in the linear isocyanate from reacting with the moisture in the epoxy resin raw material.
The invention also provides the epoxy resin prepared by the technical scheme, wherein the epoxy resin is a light yellow transparent solid, the epoxy value is 0.15-0.20 mol/100g, and the softening point is 60-80 ℃. The epoxy resin can also be used together with an epoxy curing agent to further increase the toughness and impact strength of the epoxy product.
The dendritic epoxy resin and the preparation method thereof provided by the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Adding 100g E-20 epoxy resin into a 250ml three-neck flask, introducing nitrogen into the three-neck flask, removing air, and sealing; heating the epoxy resin raw material to 80 ℃ by using an oil bath heating mode, stirring, adding 28g of methyl n-heptanoate after the epoxy resin raw material is molten, stirring uniformly, adding 0.3g of butyl phthalate, continuing to heat to 90 ℃, vacuumizing, and reacting for 2 hours at a stirring speed of 500r/min to obtain the dendritic epoxy resin.
Example 2
Adding 90g E-20 epoxy resin into a 250ml three-neck flask, introducing nitrogen into the three-neck flask, removing air, and sealing; heating the epoxy resin raw material to 90 ℃ by using an oil bath heating mode, stirring, adding 27g of 5-phenyl methyl valerate after the epoxy resin raw material is molten, uniformly stirring, adding 0.2g of dibutyltin oxide, continuously heating to 100 ℃, vacuumizing, and reacting for 3 hours at a stirring speed of 600r/min to obtain the dendritic epoxy resin.
Example 3
Adding 110g E-20 epoxy resin into a 250ml three-neck flask, introducing nitrogen into the three-neck flask, removing air, and sealing; heating the epoxy resin raw material to 110 ℃ by using an oil bath heating mode, stirring, vacuumizing to remove water in the epoxy resin raw material, adding 30g of hexyl monoisocyanate after the epoxy resin raw material is molten, stirring uniformly, adding 0.4g of zinc acetylacetonate, continuously heating to 130 ℃, and reacting for 4 hours at a stirring speed of 700r/min to obtain the dendritic epoxy resin.
Weighing and mixing the dendritic epoxy resin prepared in the embodiment 1-3 and the E-20 epoxy resin according to the formula in the table 1, uniformly mixing, extruding in an extruder, grinding into powder and sieving with a 180-mesh sieve to prepare corresponding powder coating; then, electrostatic spraying was performed, curing was performed at 200 ℃/15min, and the properties were tested, as detailed in table 2.
TABLE 1 formulation of epoxy articles
TABLE 2 Properties of epoxy articles
As can be seen from the data in tables 1 and 2, the epoxy resin in the prior art and the dendritic epoxy resin prepared by the application are cured according to the same formula and method, the flexibility of the epoxy product prepared by the dendritic epoxy resin is 2mm, the impact strength reaches over 530N cm, and the epoxy product is superior to the epoxy product prepared by the common epoxy resin and has better flexibility and impact strength.
The embodiments can show that the preparation method of the dendritic epoxy resin is simple to operate, the macromolecular branched chain is grafted to the hydroxyl position of the epoxy resin by adopting a simple process, the molecular regularity of the epoxy resin can be reduced, the movement space of a molecular chain is enlarged, and therefore the toughness and the impact resistance of the epoxy resin are improved and are superior to those of the prior art.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A preparation method of dendritic epoxy resin comprises the following steps:
mixing an epoxy resin raw material, a grafted side chain compound and a catalyst, and carrying out grafting reaction to obtain dendritic molecular epoxy resin;
the grafted side chain compound is linear chain carboxylate and/or linear chain isocyanate;
the structural formula of the linear chain isocyanate is shown as the formula I:
R1-N ═ C ═ O formula I
Wherein R is1Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane;
the linear carboxylic ester is linear carboxylic methyl ester, and the structure of the linear carboxylic ester is shown as a formula II:
wherein R is2Is phenyl-substituted C3-C15 linear alkane, biphenyl-substituted C3-C15 linear alkane, naphthyl-substituted C3-C15 linear alkane or unsubstituted C3-C15 linear alkane;
the catalyst is one or more of organic tin, titanate and acetylacetone salt;
the mass ratio of the epoxy resin raw material, the grafted side chain compound and the catalyst is (90-110): (27-30): 0.1-0.5).
2. The method of preparing a dendritic epoxy resin according to claim 1, characterized in that: the straight-chain isocyanate is hexyl monoisocyanate, 6-phenyl monoisocyanate octyl, 4-phenyl monoisocyanate butyl, 1-butylidene naphthalene monoisocyanate, 1-methyl-6-pentylidene naphthalene monoisocyanate, 4-hexylidene biphenyl monoisocyanate or 4-ethyl-4-propylidene biphenyl monoisocyanate.
3. The method of preparing a dendritic epoxy resin according to claim 1, characterized in that: the linear chain methyl carboxylate is methyl n-heptanoate, methyl 3-phenylbutyrate, methyl 5-phenylpentanoate, methyl 1-naphthylene octanoate, methyl 1-ethyl-6-butylene naphthalene carboxylate, methyl 4-hexylene biphenyl carboxylate or methyl 3-ethyl-4-butylene biphenyl carboxylate.
4. The method of preparing a dendritic epoxy resin according to claim 1, characterized in that: the organic tin catalyst is dibutyltin oxide and/or dibutyltin dilaurate;
the titanate catalyst is tetraisopropyl titanate and/or butyl titanate;
the acetylacetone salt catalyst is zinc acetylacetonate.
5. The method of preparing a dendritic epoxy resin according to claim 1, characterized in that: the temperature of the grafting reaction is 80-150 ℃, and the time of the grafting reaction is 1-4 h.
6. The dendritic epoxy resin prepared by the preparation method of any one of claims 1 to 5, which has an epoxy value of 0.15 to 0.20mol/100g and a softening point of 60 to 80 ℃.
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| CN1058604A (en) * | 1990-08-02 | 1992-02-12 | 岳阳石油化工总厂研究院 | Catalpa oil epoxy resin toughening agent and preparation method of modified epoxy resin thereof |
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| 端异氰酸酯基聚醚接枝环氧树脂的性能研究;蔡浩鹏 等;《武汉理工大学学报》;20061125;第28卷(第11期);第5-7页 * |
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